Ray was born and raised in Decatur, Georgia, and went on to begin college at Vanderbilt University. After a year at Vanderbilt, Ray returned to the Atlanta area to continue her education at Emory University. Ray graduated from Emory in 1986 with majors in English and Religion. Together with Emily Saliers she is "The Indigo Girls" in 1993.

On March 6, 2001 she released her first solo album, Stag, a southern and punk rock album. On April 12, 2005, Ray released Prom, and on December 19, 2006, she released Live from Knoxville. Her fourth solo album, Didn't It Feel Kinder, was released on August 5, 2008.

Ray is also an activist involved in multiple political and social causes, including gay rights, abortion rights, Native American rights, low-power broadcasting, women's rights, indigenous struggles, gun control, the Zapatista movement, environmental protection and the anti-death penalty movement among others. She has made several trips to Chiapas, Mexico to support the Zapatista Army of National Liberation.

She currently lives in the foothills of North Georgia.